Elsen Andrea M, Burdyńska Joanna, Park Sangwoo, Matyjaszewski Krzysztof
Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
ACS Macro Lett. 2013 Sep 17;2(9):822-825. doi: 10.1021/mz400428e. Epub 2013 Sep 4.
The design and synthesis of a powerful ligand is reported for use in activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) in miniemulsion. The structure of ',″-dioctadecyl-',″-bis[2-(4-methoxy-3,5-dimethyl)pyridylmethyl]ethane-1,2-diamine (DOD-BPED*) was formulated to produce a tetradentate ligand which was both hydrophobic and highly active. Studies in homogeneous ARGET ATRP with CuBr/DOD-BPED* demonstrated a high degree of control, similar to those ligands traditionally used. CuBr/DOD-BPED* also proved itself to be extremely useful in ARGET ATRP miniemulsion systems, at concentrations of catalyst as low as 50 ppm while maintaining control over the polymerization of butyl methacrylate (BMA). Additionally, the catalyst was tested over a range of degrees of polymerization, DP = 2000-10 000, all of which resulted in successful polymerizations. Most notably, high molecular weight polymers with > 700 000 and / < 1.4 were prepared with only 50 ppm of CuBr/DOD-BPED* catalyst under miniemulsion conditions.
报道了一种用于微乳液中电子转移活化剂再生原子转移自由基聚合（ARGET ATRP）的强效配体的设计与合成。“，”-二辛基-“，”-双[2-（4-甲氧基-3,5-二甲基）吡啶基甲基]乙烷-1,2-二胺（DOD-BPED*）的结构经设计可生成一种既疏水又具有高活性的四齿配体。在以CuBr/DOD-BPED进行的均相ARGET ATRP研究中，显示出与传统使用的那些配体相似的高度可控性。CuBr/DOD-BPED在ARGET ATRP微乳液体系中也证明了自身的实用性，在催化剂浓度低至50 ppm时仍能控制甲基丙烯酸丁酯（BMA）的聚合反应。此外，该催化剂在一系列聚合度（DP = 2000 - 10000）范围内进行了测试，所有测试均实现了成功聚合。最值得注意的是，在微乳液条件下，仅使用50 ppm的CuBr/DOD-BPED*催化剂就制备出了分子量大于700000且分散度小于1.4的高分子量聚合物。
